Academic literature on the topic 'Ni-P alloy coatings'

The present paper considers the comparative study of tribological characteristics of various electroless alloy coatings viz. Ni-P, Ni-P-W and Ni-P-Cu. The tribological behavior of these coatings depends on various parameters like load, speed, lubricant, chemical compositions and heat treatment temperature to a great extent. One of the main effects of heat treatment on these coatings is phosphide precipitation, which makes them suitable for anti-wear applications. The property of binary Ni-P can be further improved by depositing third particles electrolessly. The phase structure of the coatings depends on the amount of phosphorous and heat treatment temperature. The tribological behavior of heat treated samples reveals that Ni-P-W deposit shows higher coefficient of friction and lowest wear among these three types coatings. Very high tungsten concentration retard the phosphide precipitation, thus low concentration of tungsten and low heat treatment temperature produce better coating. In case of Ni-P-Cu, medium concentration of copper and medium heat treatment temperature produces better coating.

In order to obtain more excellent performance of composite coating, a layer of Ni-P alloy was plated firstly, then Ni-P-PTFE composite coatings was plated. If plating time ratio of electroless plating Ni-P alloy and Ni-P-PTFE composite plating was properlly controlled, performance of pure Ni-P-PTFE composite coating could be improved. The study have shown that the total plating time is 2 hours, and the plating time ratio is 1:1, and good bonding strength with the substrate, right hardness, low friction coefficient, good corrosion resistance of Ni-P /Ni-P-PTFE composite coatings have been obtained.

The Ni-Me-P alloy coatings containing metal as alloying component (Me = Co, W) in a Ni-P amorphous matrix, were potentiostatically electrodeposited onto a polycrystalline Cu substrate. Deposition potential was established based on polarization curves of electrodeposition of Ni-Co-P, Ni-W-P and Ni-P alloy coatings. SEM, EDS, XRD and X-ray microanalysis methods, were applied for chemical and physical characterization of the obtained coatings. Linear analysis of Ni, Co and W distribution in the microregions of the appropriate alloy coating revealed that surface distribution of these elements is homogeneous what is due to a molecular mixing of the amorphous nickel matrix with the alloying components. It was found that the Ni-Co-P and Ni-W-P coatings have the amorphous structure like the Ni-P deposit and alloying components as Co or W are built-in into the appropriate coating in the amorphous form. The mechanism of the induced codeposition of these ternary Ni-Me-P coatings, has been discussed.

The Ni-alloy/CrN nanolayered coatings, Ni-Al/CrN and Ni-P/CrN, were deposited on (100) silicon wafer and AISI 420 stainless steel substrates by dual-gun sputtering technique. The influences of the layer microstructure on corrosion behavior of the nanolayered thin films were investigated. The bilayer thickness was controlled approximately 10 nm with a total coating thickness of . The single-layer Ni-alloy and CrN coatings deposited at were also evaluated for comparison. Through phase identification, phases of Ni-P and Ni-Al compounds were observed in the single Ni-alloy layers. On the other hand, the nanolayered Ni-P/CrN and Ni-Al/CrN coatings showed an amorphous/nanocrystalline microstructure. The precipitation of Ni-Al and Ni-P intermetallic compounds was suppressed by the nanolayered configuration of Ni-alloy/CrN coatings. Through Tafel analysis, the and values ranged from –0.64 to –0.33 V and to A/, respectively, were deduced for various coating assemblies. The corrosion mechanisms and related behaviors of the coatings were compared. The coatings with a nanolayered Ni-alloy/CrN configuration exhibited a superior corrosion resistance to single-layer alloy or nitride coatings.

The Ni-P coatings were deposited on AM60 magnesium alloy by electroless plating process without or with accelerators. Without accelerators, the deposition rate is slow and required high bath temperature to obtain compact coating. There have many defects on the surface of the Ni-P coatings which deposited at high bath temperature. The composite accelerators were introduced into the bath for improving the growth rate and the quality of the Ni-P coating. Uniform, with no pores or cracks, “cauliflower-like” structure and complete Ni-P coatings were deposited only taken 20 min with additives at low bath temperature. The XRD result indicates that the structure of the Ni-P coating is amorphous nickel. The corrosion test results indicated that the corrosion resistance of this coated AM60 magnesium alloys increases distinctly as compared to bare alloys.

This paper describes the performance of Ni-P and Ni-Mo-P alloy coatings deposited by electroless plating on the aluminum alloy 5052 to evaluate the corrosion resistance, thermal stability and electro-conductivity of coating assemblies. Corrosion behaviors of the obtained deposits in a 0.5M H2SO4 environment were investigated. The crystalline state and morphologies of Ni-P and Ni- Mo-P alloys were examined by field emission scanning electron microscopy (FE-SEM). The experimental results indicate that the Ni-Mo-P coating operated at 70°C and pH 9.0 has a nanocrystalline structure and its corrosion resistance in a 0.5M H2SO4 environment can be enhanced by the co-deposition of Mo as compared to Ni-P films. It has also been found that the Ni-Mo-P ternary alloys reveal good thermal stability after annealing at 400°C. Based on the excellent performance of Ni-Mo-P ternary alloys, these alloys have a potential to be applied to precision mould, optical parts mould, and surface metallization of substrates.

The purpose of the present study is to evaluate the effect of the electroless Ni-P/diamond/graphene composite coating on the structure and surface hardness of 2024-T6 aluminum alloy as well as their effect on the corrosion and wear resistance of the alloy in 3.5 % NaCl solution. The electroless Ni-P plating solution was prepared by adding different size diamond (6-12 μm and 0.2 μm) and nanographene into the electroless Ni-P plating solution to obtain Ni-P/diamond, Ni-P/graphene and Ni-P/daimond/graphene composite coatings for comparison. Experimental results indicated that the Ni-P/diamond, Ni-P/graphene and Ni-P/daimond/graphene composite coatings can be successfully electroless deposited on anodized 2024-T6 aluminum alloy. The anodically oxidized films, that formed on the aluminum alloy using phosphoric acid as the electrolyte, was porous with high density of pores, and thus could enhance the adhesion of the composite coatings. The Ni-P/daimond/graphene hybrid coating had a higher hardness as well as better corrosion and wear resistance of 2024-T6 alloy in 3.5 wt.% NaCl solution as compared with other composite coatings. When the combination of nanographene and smaller diamond particles added this beneficial effect was significantly raised, especially the composite coating was further vacuum annealed at 400 °C for 24 h to obtain a more smooth and defect-free coating structure.

Electroless Ni-Zn-P coating with the optimal content of Ni and Zn in the alloy provides high corrosion resistance for steel. Ni-rich phase of this high hardness Ni-Zn-P alloy offers barrier protection property and sacrificial protection property is obtained from the alloy with proper content of Zn. In this work, the Ni-Zn-P coatings were prepared on steel substrates by using alkaline electroless deposition. The parameters of deposition process including complexing agent concentration, bath pH, zinc ion and nickel ion concentration were systematically studied. The microstructural morphology and elemental composition of the coatings were characterized by scanning electron microscopy. It was found that complexing agent, zinc ion and nickel ion concentrations play important role on Zn content of Ni-Zn-P alloy whereas alkalinity of the solution bath directly affects the deposition rate. The results of corrosion resistance investigated by linear polarization illustrate that the corrosion potential (Ecorr) of Ni-Zn-P coatings is negatively shifted by an increase of Zn content in the alloys. From this work, Ecorr of 83%Ni-11%Zn-6%P coating prepared in this system is slightly lower than steel. To achieve a higher effect of sacrificial protection for corrosion protection of steel, Ni-Zn-P with higher content of Zn should be further studied.

The corrosion behavior of duplex Ni-P coatings deposited on AZ91 magnesium alloy was studied. The electroless deposition process of duplex Ni-P coating consisted in the preparation of low-phosphorus Ni-P coating (5.7 wt.% of P), which served as a bond coating and high-phosphorus Ni-P coating (11.5 wt.% of P) deposited on it. The duplex Ni-P coatings with the thickness of 25, 50, 75 and 100 µm were deposited on AZ91 magnesium alloy. The electrochemical corrosion behavior of coated AZ91 magnesium alloy was investigated by electrochemical impedance spectroscopy and potentiodynamic polarization method in 0.1 M NaCl. Obtained results showed a significant improvement in the corrosion resistance of coated specimens when compared to uncoated AZ91 magnesium alloy. From the results of the immersion tests in 3.5 wt.% NaCl, 10% solution of HCl and NaOH and 5% neutral salt spray, a noticeable increase in the corrosion resistance with the increasing thickness of the Ni-P coating was observed.

The aim of this diploma thesis was summary of all steps and knowledge necessary to deposition of quality Ni-P coatings deposited on wrought magnesium alloys AZ31 and AZ61. There is the treatise about wrought magnesium alloys AZ31 and AZ61. Thesis includes its phase composition in the theoretical part. There are given its possible processing methods too. Next, there is desribed the mechanism of deposition of Ni-P coatings, components required to electroless deposition and factors affecting the quality and properties of these coatings. The theoretical part is ended by serie of reviews. Authors of these reviews deal with pretreatment of substrates, preparation, characterization and measuring of mechanical, structure and corrosion properties of deposited coatings. The optimalization of pretreatment, parametres and composition of nickel bath suitable for magnesium alloys is described in experimental part. The microstructure, present interlayer between substrate and Ni-P coating and chemical composition of deposited coatings was observed and measured by optical and electron microscopy. The mechanical characterization of Ni-P coatings was performed by microhardness tester.

Cílem této diplomové práce jse najít nejnižší možnou tloušťku nikl-fosforového povlaku, který může být galvanicky pokoven mědí bez defektů na horčíkové slitině, nikl-fosforového nebo měděného povlaku. V teoretické části jsou shrnuty poznatky o hořčíkových slitinách a jejich korozi. Navíc se teoreticá část zaměřuje na popis procesu bezproudého niklování a elektrochemického pokovování mědí a jejich porovnání. Na konci teoretické části je shrnut současný výzkum o elektrochemickém pokovování hořčíkových slitin. V experimentální části byl popsán proces přípravy povlaků Ni-P a Cu na horčíkové slitině AZ91. Na jedné vrstvě a dvojité vrstvě Ni-P povlaku byla provedena elektrodepozice mědi. Navíc byl diskutován vliv předůpravy před samotnou elektrodepozicí mědi. Za účelem zjištění korozních vlastností vzorků byl vykonán potenciodynamický test. Následně byly připraveny metalografické výbrusy jednotlivých vzorků a pomocí světelného a rastrovacího elektronového mikroskopu byla provedena charakterizace. Na konec bylo zjištěno prvkové složení jednotlivých povlaků pomocí EDX analýzy.

碩士
國立聯合大學
材料科學工程學系碩士班
99
In the study, the ternary Ni-Ru-P alloy coatings are fabricated by magnetron dual-gun co-sputtering technique. The chemical composition variation of the coatings in terms of sputtering parameters, including input power, process temperatures and Ar gas flow rate are investigated. The Ni-Ru-P coatings with a Ru content <38.9 at.% remain an amorphous/nanocrystalline feature under a vacuum annealing temperature up to 500oC. On the other hand, Ni(Ru) and Ni-P precipitation phases form as annealing temperature is raised to 550oC. With Ru content >52.7 at.%, the as-fabricated Ni-Ru-P coating shows crystallized Ni + Ru + Ru2P mixed phases. Such phase distribution for high Ru-content ternary Ni-Ru-P is stable under annealing temperature up to 600oC. The crystallized Ni + Ru + Ru2P phases are also responsible for the slight increase in surface roughness. The hardness for low Ru contents as-deposited films distributed around 7.2 to 8.1 GPa. The coatings with crystallized Ru and Ru2P phases possess a higher hardness value of 10.4 GPa. Limited oxide penetration less than 20 nm at Ni29.5Ru64.6P5.9 coating surface is confirmed. The Ni + Ru + Ru2P phases distribution resulted from high content Ru co-sputtering is beneficial to oxidation resistance. The introduction of high Ru concentration significantly strengthens the mechanical and anti-oxidation behaviors of Ni-P-based coating. The Ru can improve the corrosion resistance of binary Ni-P coating from the electrochemical analysis. The effect of W, Al and Ru elements in Ni-P-based coating on their mechanical properties and characteristics are discussed.

碩士
健行科技大學
機械工程系碩士班
103
Ni-Mo-P alloy coatings were deposited on AA5083 aluminum alloy by electroless deposition for wear and corrosion properties. we hope Ni-Mo-P alloy coatings more hard and smooth then before by vacuum heat treatment . The AA5083 aluminum alloy is widely used for many application in automotive , marine , aircraft body sheet due to its excellent combination of strength, corrosion resistance . Research step : 1. Ni-Mo-P and Ni-P coatings were deposited on AA5083 aluminum alloy by electroless deposition . 2. Different temperature and time variables in vacuum heat treatment. 3. The coatings are deposited for characterizations of microhardness , wear and corrosion test . Coating''s hard is strength by vacuum heat treatment , but find some pits on coatings surface , this properties not conducive in corrosion test. Electroless Ni-Mo-P were deposited in pH 6.8 60 min 83 5 . Ni-Mo-P coatings due to its excellent combination of corrosion resistance in 200 15min vacuum heat treatment.

Magnesium and its alloys are extensively used for various industries such as aerospace, automobile and electronics due to their excellent properties such as low density, high strength and stiffness and electromagnetic shielding. However, the wide spread applications of these alloys are limited due to the undesirable properties such as poor corrosion, wear and creep resistance and high chemical reactivity. These alloys are highly susceptible to galvanic corrosion in sea water environment due to their high negative potential (-2.37 V vs SHE). The effective way of preventing corrosion is through the formation of a protective coating, which acts as a barrier between the corrosive medium and the substrate. Many surface modification methods such as electro/ electroless plating, conversion coating, physical and chemical vapour depositions, thermal spray coating etc., are available currently to improve the corrosion resistance of Mg alloys. Of these methods, the electroless nickel plating has gained considerable importance because of its excellent properties such as high hardness, good wear and corrosion resistance. The properties of binary electroless nickel coating have been further improved by the addition of a third element such as cobalt, tungsten, tin and copper etc. It has been reported that the addition of tungsten as the third element in the Ni-P improves the properties such as hardness, wear and corrosion resistance, thermal stability and electrical resistance. Magnesium alloys are categorized as a “difficult to plate metal”, because of their high reactivity in the aqueous solution. They react vigorously with atmospheric oxygen and water, resulting in the formation of the porous oxide/ hydroxide film which does not provide any protection in the corrosive environment. Further, the presence of this oxide film prevents the formation of a good adhesive bond between the coating and the substrate. The surface treatment process for removal of the oxide layer is very much essential before plating the Mg alloy. Currently two processes such as zinc immersion and direct electroless nickel plating are adopted to plate Mg alloys. Etching in a solution of chromate and nitric acid followed by immersion in HF solution to form a conversion film is necessary for direct electroless nickel (EN) plating of Mg alloy. However, strict environmental regulations restrict their usage because of hazardous nature. Expensive palladous activation treatment is a well-known process as a replacement for chromate-HF pretreatments for Mg alloys. It has been reported that EN plating has been carried out over Mg alloys by using conversion coating followed by HF treatment. Formation of an intermediate oxide layer by electrolytic methods is also one of the ways these toxic pretreatments can be avoided. Microarc oxidation (MAO) is an environment friendly surface treatment technique which provides high hardness, better corrosion and wear resistance properties for the Mg alloys. EN coating has been prepared on MAO layer for improving the corrosion resistance. These MAO/EN composite coatings have been prepared using chromic acid and HF pretreatment process. As the replacement for the chromate-HF pretreatment, SnCl2 and PdCl2 sensitization and activation procedures respectively were adopted over MAO layer for the deposition of Ni-P coating. From the above reported literature, it can be inferred that for the activation of inert MAO layer to deposit electroless nickel coating, the hazardous chromate/HF and highly expensive PdCl2 activation processes were followed. Therefore, there is a need for identifying an alternative simple and cost effective pretreatment process for the deposition of electroless nickel. It is well known that borohydride is a strong reducing agent that has been used for the deposition of Ni-B coatings. In the present study, an attempt has been made to utilize borohydride in the pretreatment process for the reduction of Ni2+ ions over the MAO interlayer, which provides the nucleation sites for the deposition of Ni-P coating. Ni-P and Ni-P/Ni-W-P duplex coatings were deposited from stabilizer free carbonate bath on AZ31B Mg alloy to improve the corrosion resistance of the base substrate. The conventional chromate and HF pretreatment processes were followed for the deposition of electroless nickel coating. In order to improve the corrosion resistance of the duplex coating, post treatments such as heat treatment (4 h at 150°C) and chromate passivation were adopted. EDX analysis of AZ31B Mg alloy showed the presence of 2.8 wt.% of Al and 1.2 wt. % Zn with the balance of Mg for AZ31B Mg alloy. After the chromic acid and HF treatment, the magnesium content was reduced from 90.0 wt % to 54.9 wt%, which could be due to the incorporation of chromium on the surface layer. The surface showed about 17.8 wt. % of F. The alloy exhibited the roughness of about 0.29± 0.01µm after mechanical polishing. The roughness value was significantly changed after the chromic acid treatment processes. The maximum roughness of about 1.28±0.06 µm was obtained after the HF activation. XPS analysis confirmed the existence of chromium in +3 oxidation state after the chromic acid treatment. The Ni-P coating thickness of about 25 microns was obtained in 1 h and 15 min. In the case of duplex coatings, Ni-P plating was done for 45 min. to obtain approx. 17 microns thickness and Ni-W-P plating was done for 1.15 h to obtain a thickness of approx. 10 microns, resulting in a total thickness of 25 ± 5 microns. Ni–P coating exhibited nodular morphology with porosity. The size of these cluster nodules were of about 10 µm in diameter. On the other hand, the duplex coating exhibited a less nodular, dense and smooth appearance. From the compositional analysis it was found that Ni–P coating contained about 6 wt. % P. In the case of duplex coating, the P content was reduced to 3 wt % due to the incorporation of about 2 wt% of tungsten. In corrosion studies, the potentiodynamic polarization data obtained for bare Ni-P coating in 0.15 M NaCl solution exhibited a higher current of about 218 μA/cm2 as compared to the substrate due to the porosity of the coating. However, the Ni-P/Ni-W-P duplex showed 55 times improvement in corrosion resistance, vis-a-vis Ni-P due to the dense nature of the coating. The corrosion resistance of the coatings increased in the following order: Ni-P < bare alloy < duplex < duplex-passivated < duplex-heat treated passivated. In EIS study, the Nyquist plot obtained for the bare substrate and Ni–P coating showed the presence of inductance behavior at the lower frequency region due to the adsorption of electroactive species over the substrate through the porous oxide layer. However, the passivated and duplex passivated coatings exhibited only capacitive behavior due to their compact nature. From the above, it can be concluded that, direct deposition of Ni-P coating over the chosen Mg alloy using chromic acid and HF pretreatment process resulted in porous morphology, which affected the corrosion resistance of the coating. As an alternative strategy, the microarc oxidation conversion coating was developed on Mg alloy and characterized. The MAO coating was developed using silicate electrolyte at three different current densities (0.026, 0.046 and 0.067 A/cm2) for about 15 min. With respect to the MAO coating, an increase in the current density increased the pore diameter and decreased the pore density. The surface of the coating became coarser and rough. The cross-sectional morphology of the coating showed two district layers namely the dense and thin inner layer and a porous thick outer layer. The thickness of the coating increased with increase in current density. MAO coating prepared at an intermediate current density of 0.046 A/cm2 exhibited a higher thickness of about 12 µm and a further increase in current density showed a decrease in thickness, due to the greater rate of dissolution of Mg, relative to the rate of deposition. The surface roughness of the MAO coatings also increased with increase in current density. The Ra value increased from 1.39±0.06 to 3.52±0.17 µm with increase in current density. XRD peaks obtained for the Mg substrates corresponded predominately to magnesium. However, the coated specimens showed the presence of peaks corresponding to Mg2SiO4 along with Mg and MgO. The corrosion measurements for the bare substrate and MAO coatings were carried out in 3.5% NaCl medium (0.6 M). Based on potentiodynamic polarization studies, the MAO coating prepared at 0.046 A/cm2 exhibited a lower corrosion current density with a higher Rp value, which was about five orders of magnitude higher than the bare substrate, due to the dense nature of the coating. In EIS study, MAO coatings were fitted with the two time constants equivalent circuit containing outer porous layer and inner barrier layer. The barrier layer resistance values were higher than that of porous layer resistance, which indicated that the resistance offered by barrier layer was higher than the porous layer. The total resistance value obtained for the coating prepared at 0.046 A/cm2 were higher compared to the other coatings, which attested to its better corrosion resistance. The electrochemical noise measurement was carried out for longer immersion durations upto 336 h in 3.5% NaCl solution. The noise resistance value obtained for the base Mg alloy was about 100 Ω at 1h immersion, whereas for the MAO coating prepared at 0.04 A/cm2 a maximum value of about 34.8 MΩ was achieved and it was retained even after 96 h of immersion. Mott–Schottky analysis showed that the oxide layer on magnesium substrate acted as a n-type semiconductor, whereas the MAO coatings exhibited p-type semiconductor behavior. The MAO coating obtained at an intermediate current density showed a higher acceptor density and the flat band potential, which resulted in the better performance of the coating in corrosive environment. In another set of investigations, the Ni-P and Ni-P/Ni-W-P coatings were deposited on AZ31B Mg alloy with MAO coating as an interlayer. The MAO layer was activated by a simple borohydride pretreatment process. During the pretreatment process, the MAO coating was subjected to mild alkali treatment, immersion in the Ni-P plating solution and finally immersion in borohydride solution. During each pretreatment step, the sample was characterized for their surface morphology and composition. The surface morphology showed the distribution of spherical particles over the surface of MAO coating after immersion in the Ni-P plating solution. EDX analysis showed the presence of 2.4 wt. % of Ni, which confirmed that Ni ions were adsorbed over the surface of the MAO coating during the pretreatment process. XPS analysis carried out after immersion in the Ni-P plating solution indicated that Ni existed in +2 oxidation state. The surface became smooth and uniform with flake- like morphology after the borohydride treatment, which indicated that the surface was etched by the borohydride solution. EDX analysis showed the presence of 1.8 wt.% of Ni after borohydride reduction. XPS analysis confirmed the reduction of nickel to the zero oxidation state. Additionally, MAO/Ni-P and MAO/Ni-P/Ni-W-P duplex coatings were developed on MAO coating after a simple borohydride pretreatment. Ni-P and duplex coatings showed uniform and dense nodular morphology without any defects, which clearly indicated that the borohydride treatment provided a uniform and homogeneous active surface for the deposition of electroless nickel based coatings. Borohydride pretreatment process resulted in excellent bonding between MAO/Ni-P layers in the cross section. Based on potentiodynamic polarization studies, the corrosion current values obtained for MAO/ Ni-P and MAO/Ni-P/Ni-W-P duplex coatings were about 1.44 and 1.42 µA/cm2, respectively. The coating showed about 97 times improvement in corrosion resistance compared to the bare substrate, attesting to the dense nature of the coating. In EIS study, the single time constant equivalent circuit was used for fitting the spectra, which pertained to the coating /electrolyte interface. The single time constant could be attributed to the pore-free dense, uniform coatings developed over the MAO interlayer. For the MAO/Ni-P and MAO/Ni-P-Ni-W-P duplex coatings, the charge transfer resistance of about 15 and 11 kΩcm2 were obtained for duplex and Ni-P coatings, which reinforce the better corrosion protective ability of the coating. The above investigation confirms that MAO coatings have good corrosion resistance in the aggressive chloride medium. Consequently, they can serve as an ideal interlayer for the deposition of the electroless nickel coating. Even if the electroless nickel coating is found to fail in harsh environments, the MAO interlayer can protect the base substrate due to its higher corrosion resistance. It is also noteworthy that the borohydride treatment provides better adhesion between the MAO/Ni-P interlayer.

Magnesium and its alloys are extensively used for various industries such as aerospace, automobile and electronics due to their excellent properties such as low density, high strength and stiffness and electromagnetic shielding. However, the wide spread applications of these alloys are limited due to the undesirable properties such as poor corrosion, wear and creep resistance and high chemical reactivity. These alloys are highly susceptible to galvanic corrosion in sea water environment due to their high negative potential (-2.37 V vs SHE). The effective way of preventing corrosion is through the formation of a protective coating, which acts as a barrier between the corrosive medium and the substrate. Many surface modification methods such as electro/ electroless plating, conversion coating, physical and chemical vapour depositions, thermal spray coating etc., are available currently to improve the corrosion resistance of Mg alloys. Of these methods, the electroless nickel plating has gained considerable importance because of its excellent properties such as high hardness, good wear and corrosion resistance. The properties of binary electroless nickel coating have been further improved by the addition of a third element such as cobalt, tungsten, tin and copper etc. It has been reported that the addition of tungsten as the third element in the Ni-P improves the properties such as hardness, wear and corrosion resistance, thermal stability and electrical resistance. Magnesium alloys are categorized as a “difficult to plate metal”, because of their high reactivity in the aqueous solution. They react vigorously with atmospheric oxygen and water, resulting in the formation of the porous oxide/ hydroxide film which does not provide any protection in the corrosive environment. Further, the presence of this oxide film prevents the formation of a good adhesive bond between the coating and the substrate. The surface treatment process for removal of the oxide layer is very much essential before plating the Mg alloy. Currently two processes such as zinc immersion and direct electroless nickel plating are adopted to plate Mg alloys. Etching in a solution of chromate and nitric acid followed by immersion in HF solution to form a conversion film is necessary for direct electroless nickel (EN) plating of Mg alloy. However, strict environmental regulations restrict their usage because of hazardous nature. Expensive palladous activation treatment is a well-known process as a replacement for chromate-HF pretreatments for Mg alloys. It has been reported that EN plating has been carried out over Mg alloys by using conversion coating followed by HF treatment. Formation of an intermediate oxide layer by electrolytic methods is also one of the ways these toxic pretreatments can be avoided. Microarc oxidation (MAO) is an environment friendly surface treatment technique which provides high hardness, better corrosion and wear resistance properties for the Mg alloys. EN coating has been prepared on MAO layer for improving the corrosion resistance. These MAO/EN composite coatings have been prepared using chromic acid and HF pretreatment process. As the replacement for the chromate-HF pretreatment, SnCl2 and PdCl2 sensitization and activation procedures respectively were adopted over MAO layer for the deposition of Ni-P coating. From the above reported literature, it can be inferred that for the activation of inert MAO layer to deposit electroless nickel coating, the hazardous chromate/HF and highly expensive PdCl2 activation processes were followed. Therefore, there is a need for identifying an alternative simple and cost effective pretreatment process for the deposition of electroless nickel. It is well known that borohydride is a strong reducing agent that has been used for the deposition of Ni-B coatings. In the present study, an attempt has been made to utilize borohydride in the pretreatment process for the reduction of Ni2+ ions over the MAO interlayer, which provides the nucleation sites for the deposition of Ni-P coating. Ni-P and Ni-P/Ni-W-P duplex coatings were deposited from stabilizer free carbonate bath on AZ31B Mg alloy to improve the corrosion resistance of the base substrate. The conventional chromate and HF pretreatment processes were followed for the deposition of electroless nickel coating. In order to improve the corrosion resistance of the duplex coating, post treatments such as heat treatment (4 h at 150°C) and chromate passivation were adopted. EDX analysis of AZ31B Mg alloy showed the presence of 2.8 wt.% of Al and 1.2 wt. % Zn with the balance of Mg for AZ31B Mg alloy. After the chromic acid and HF treatment, the magnesium content was reduced from 90.0 wt % to 54.9 wt%, which could be due to the incorporation of chromium on the surface layer. The surface showed about 17.8 wt. % of F. The alloy exhibited the roughness of about 0.29± 0.01µm after mechanical polishing. The roughness value was significantly changed after the chromic acid treatment processes. The maximum roughness of about 1.28±0.06 µm was obtained after the HF activation. XPS analysis confirmed the existence of chromium in +3 oxidation state after the chromic acid treatment. The Ni-P coating thickness of about 25 microns was obtained in 1 h and 15 min. In the case of duplex coatings, Ni-P plating was done for 45 min. to obtain approx. 17 microns thickness and Ni-W-P plating was done for 1.15 h to obtain a thickness of approx. 10 microns, resulting in a total thickness of 25 ± 5 microns. Ni–P coating exhibited nodular morphology with porosity. The size of these cluster nodules were of about 10 µm in diameter. On the other hand, the duplex coating exhibited a less nodular, dense and smooth appearance. From the compositional analysis it was found that Ni–P coating contained about 6 wt. % P. In the case of duplex coating, the P content was reduced to 3 wt % due to the incorporation of about 2 wt% of tungsten. In corrosion studies, the potentiodynamic polarization data obtained for bare Ni-P coating in 0.15 M NaCl solution exhibited a higher current of about 218 μA/cm2 as compared to the substrate due to the porosity of the coating. However, the Ni-P/Ni-W-P duplex showed 55 times improvement in corrosion resistance, vis-a-vis Ni-P due to the dense nature of the coating. The corrosion resistance of the coatings increased in the following order: Ni-P < bare alloy < duplex < duplex-passivated < duplex-heat treated passivated. In EIS study, the Nyquist plot obtained for the bare substrate and Ni–P coating showed the presence of inductance behavior at the lower frequency region due to the adsorption of electroactive species over the substrate through the porous oxide layer. However, the passivated and duplex passivated coatings exhibited only capacitive behavior due to their compact nature. From the above, it can be concluded that, direct deposition of Ni-P coating over the chosen Mg alloy using chromic acid and HF pretreatment process resulted in porous morphology, which affected the corrosion resistance of the coating. As an alternative strategy, the microarc oxidation conversion coating was developed on Mg alloy and characterized. The MAO coating was developed using silicate electrolyte at three different current densities (0.026, 0.046 and 0.067 A/cm2) for about 15 min. With respect to the MAO coating, an increase in the current density increased the pore diameter and decreased the pore density. The surface of the coating became coarser and rough. The cross-sectional morphology of the coating showed two district layers namely the dense and thin inner layer and a porous thick outer layer. The thickness of the coating increased with increase in current density. MAO coating prepared at an intermediate current density of 0.046 A/cm2 exhibited a higher thickness of about 12 µm and a further increase in current density showed a decrease in thickness, due to the greater rate of dissolution of Mg, relative to the rate of deposition. The surface roughness of the MAO coatings also increased with increase in current density. The Ra value increased from 1.39±0.06 to 3.52±0.17 µm with increase in current density. XRD peaks obtained for the Mg substrates corresponded predominately to magnesium. However, the coated specimens showed the presence of peaks corresponding to Mg2SiO4 along with Mg and MgO. The corrosion measurements for the bare substrate and MAO coatings were carried out in 3.5% NaCl medium (0.6 M). Based on potentiodynamic polarization studies, the MAO coating prepared at 0.046 A/cm2 exhibited a lower corrosion current density with a higher Rp value, which was about five orders of magnitude higher than the bare substrate, due to the dense nature of the coating. In EIS study, MAO coatings were fitted with the two time constants equivalent circuit containing outer porous layer and inner barrier layer. The barrier layer resistance values were higher than that of porous layer resistance, which indicated that the resistance offered by barrier layer was higher than the porous layer. The total resistance value obtained for the coating prepared at 0.046 A/cm2 were higher compared to the other coatings, which attested to its better corrosion resistance. The electrochemical noise measurement was carried out for longer immersion durations upto 336 h in 3.5% NaCl solution. The noise resistance value obtained for the base Mg alloy was about 100 Ω at 1h immersion, whereas for the MAO coating prepared at 0.04 A/cm2 a maximum value of about 34.8 MΩ was achieved and it was retained even after 96 h of immersion. Mott–Schottky analysis showed that the oxide layer on magnesium substrate acted as a n-type semiconductor, whereas the MAO coatings exhibited p-type semiconductor behavior. The MAO coating obtained at an intermediate current density showed a higher acceptor density and the flat band potential, which resulted in the better performance of the coating in corrosive environment. In another set of investigations, the Ni-P and Ni-P/Ni-W-P coatings were deposited on AZ31B Mg alloy with MAO coating as an interlayer. The MAO layer was activated by a simple borohydride pretreatment process. During the pretreatment process, the MAO coating was subjected to mild alkali treatment, immersion in the Ni-P plating solution and finally immersion in borohydride solution. During each pretreatment step, the sample was characterized for their surface morphology and composition. The surface morphology showed the distribution of spherical particles over the surface of MAO coating after immersion in the Ni-P plating solution. EDX analysis showed the presence of 2.4 wt. % of Ni, which confirmed that Ni ions were adsorbed over the surface of the MAO coating during the pretreatment process. XPS analysis carried out after immersion in the Ni-P plating solution indicated that Ni existed in +2 oxidation state. The surface became smooth and uniform with flake- like morphology after the borohydride treatment, which indicated that the surface was etched by the borohydride solution. EDX analysis showed the presence of 1.8 wt.% of Ni after borohydride reduction. XPS analysis confirmed the reduction of nickel to the zero oxidation state. Additionally, MAO/Ni-P and MAO/Ni-P/Ni-W-P duplex coatings were developed on MAO coating after a simple borohydride pretreatment. Ni-P and duplex coatings showed uniform and dense nodular morphology without any defects, which clearly indicated that the borohydride treatment provided a uniform and homogeneous active surface for the deposition of electroless nickel based coatings. Borohydride pretreatment process resulted in excellent bonding between MAO/Ni-P layers in the cross section. Based on potentiodynamic polarization studies, the corrosion current values obtained for MAO/ Ni-P and MAO/Ni-P/Ni-W-P duplex coatings were about 1.44 and 1.42 µA/cm2, respectively. The coating showed about 97 times improvement in corrosion resistance compared to the bare substrate, attesting to the dense nature of the coating. In EIS study, the single time constant equivalent circuit was used for fitting the spectra, which pertained to the coating /electrolyte interface. The single time constant could be attributed to the pore-free dense, uniform coatings developed over the MAO interlayer. For the MAO/Ni-P and MAO/Ni-P-Ni-W-P duplex coatings, the charge transfer resistance of about 15 and 11 kΩcm2 were obtained for duplex and Ni-P coatings, which reinforce the better corrosion protective ability of the coating. The above investigation confirms that MAO coatings have good corrosion resistance in the aggressive chloride medium. Consequently, they can serve as an ideal interlayer for the deposition of the electroless nickel coating. Even if the electroless nickel coating is found to fail in harsh environments, the MAO interlayer can protect the base substrate due to its higher corrosion resistance. It is also noteworthy that the borohydride treatment provides better adhesion between the MAO/Ni-P interlayer.

The Ni-P alloy coatings are widely studied due to their superior mechanical and tribological properties. Ni-P coatings are also considered to be a viable alternative to the chromium (Cr) coatings which utilize environmentally hazardous and toxic carcinogenic electrolytic solutions. The current work focuses on strategies to enhance the corrosion resistance performance of electrodeposited Ni-P coatings primarily by incorporation of foreign additives (carbon nanotubes (CNTs) and graphene) and by engineering of the Ni-P micro-texture and phase fraction (crystalline and amorphous phases). Nickel-phosphorus (Ni-P) coatings were electrodeposited over mild steel substrate using DC power source in conventional two electrode electrochemical setup. As-deposited Ni-P coatings were subjected to phase, microstructural and morphological characterizations using x-ray diffraction, electron microscopy and electron backscatter diffraction techniques. The corrosion analysis was accomplished by using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarisation techniques (Tafel plot) in 3.5 wt.% NaCl solution. Key observations are: (a) in the work on the incorporation of CNTs and Graphene in Ni-P coatings, it was observed that an optimum volume fraction of the additives yielded high corrosion resistance performance. This was essentially due to the smooth compact and defect free surface morphology, (b) in the work on the correlation between micro-texture and corrosion behaviour of Ni-P coatings as a function of phosphorous content, it was observed that the phosphorous concentration range where the nano-crystalline region (along with the minor amorphous phase fraction) was dominant a slight alteration in texture determines the corrosion rate. With increase in the amorphous region, the galvanic coupling between the anodic amorphous phase and cathodic crystalline phase determined the corrosion behaviour. A mixture of amorphous and crystalline phases with lower fraction of the amorphous phase enhanced the corrosion rate due to increased galvanic coupling. For higher addition of phosphorus, large fraction of amorphous phase evolved which significantly reduced the galvanic coupling leading to higher corrosion resistance behaviour, (c) in the work on the effect of deposition temperature (bath temperature of 15˚C, 20˚C, 25˚C, 35˚C) on the evolution of correlation between texture and corrosion behaviour of Ni-P coatings, it was observed that the coating deposited at 15°C and 25°C yielded the maximum and minimum corrosion rate respectively. Analysis of the coating texture revealed that the higher corrosion rate for the 15°C coating was due to low fraction of low energy low angle grain boundaries (LAGBs), higher strain within the grains, and (101) growth texture. Lower corrosion rate, on the other hand, for the 25°C coating was due to low energy (001) growth texture, low average strain within the grains, and high fraction of LAGBs, (d) in the work on the effect of deposition current density on the evolution of correlation between texture and corrosion behaviour of Ni-P coatings, it was observed that the Ni-P coating (deposited using 60 mA.cm-2) that exhibited the lowest corrosion rate was characterized by the presence of lower energy surface texture, lower grain size, narrow grain size distribution and a relatively higher fraction of low energy Σ3 coherent twin boundaries. A higher corrosion rate for coating deposited using 5 mA.cm-2 was due to higher energy surface texture and larger grain size distribution.

碩士
健行科技大學
機械工程系碩士班
103
This study used electroless plating process to prepare Ni-P-Cu composite coating on AA7075 aluminum alloy surface after anodizing treatment. The Stress-Corrosion Cracking (SCC) charactenrstics for the coating in 3.5%NaCl aqueous solution via slow strain rate test was also studied. The surface morphology, element composition and surface hardness of the coatings were analyzed by SEM, EDS and Vicker’s hardness tester. The corrosion and wear-corrosion resistance of electrolessplating Ni-P-Cu composite coating in 3.5% NaCl aqueous solution was evaluated, and also analyzed by electrochemical polarization measurement. Experimental results indicated that electrolessplating Ni-P-Cu composite coating has high hardness, good corrosion resistance, particularly owing to the anodizing treatment of aluminum alloy. The anodizing treatment of AA7075 aluminum alloy substrate efficiently improved the adhesion, surface morphology and hardness of the electroplated Ni-P-Cu composite coating. The results also indicated that the anti-SCC of the coating is potentiodynamic polarization significantly increased in 3.5% NaCl aqueous solution.

碩士
清雲科技大學
機械工程研究所
98
The purpose of this study is to evaluate the corrosion and wear-corrosion resistance properties of electroless Ni/nano-TiO2 and Ni/CNT plated nano-composite coatings on AA5083 alloy in 3.5 wt.% NaCl solution. The nano-composite coatings were prepared by electroless plating method that the nano-TiO2 (15 nm) and Carbon nano-tube (CNT, 5nm) particles were added into the eletroless Ni plating solution with a low and a high concentration of 1 g/L and 10 g/L for comparison, respectively. The corrosion resistance properties of the nano-composite coatings were examined by both potentiodynamic polarization and immersion corrosion test. The experimental results indicated that both Ni/nano-TiO2 and Ni/CNT nano-composite coatings exhibited an uniform and a compact surface morphology, not only improving the corrosion and wear-corrosion resistance of the AA5083 Al-Mg alloy but also superior to the electroless Ni-P coating. Both the corrosion and wear-corrosion resistance of the nano-composite coatings were enhanced significantly at high concentration of 10 g/L, in addition that the CNT added was superior to the nano-TiO2 added electroloss plating solution.

High efficacy and industrial applicability on electrocatalytic hydrogen production is achieved by proper furnishing of components in the reaction cell. The idea on the basic mechanism of hydrogen evolution reaction (HER), efficient modification of available systems, and recent trends in the development strategies of suitable materials are very important to be explored to design novel systems for large-scale production. This review chapter discusses the scientific details on electrocatalytic HER and plausible materials used for catalyzing the reaction. And it outlines the trends in design and development of transition metal-based catalytic coating systems with a special focus on Ni-P alloy coating and scientific aspects of the methods and the materials used for the HER. On the whole, the discussion on HER and its catalytic systems provides an insight of their potential to be explored for enhanced energy production in hydrogen fuel cell technology for stationary and industrial applications.

Abstract The aim of this study was to improve the properties of atmospheric plasma sprayed WC - Co - Ni coatings by post treatment with induction heating. The spray powders used were WC - Co - Ni composite powders, produced by adding Ni - P alloy to WC - Co powder. Induction heating applied to the coating caused fusion of the Ni - P alloy with the WC - Co - Ni coating and a strong metallurgical bond with the steel substrate. An innovation in recent experiments was the use of an antioxidant paste applied to the outer surface of the coating under treatment. This eliminated the need for working under the restrictions of a hydrogen gas environment. The properties of the treated coating were investigated regarding microstructure, hardness, adhesive strength, abrasion resistance and porosity.

Nickel phosphorus (Ni-P) coatings possess tailored mechanical and anticorrosion properties and have found applications in industries like automotive, oil and gas, electronics, and aerospace. Their properties can further be enhanced by incorporating nanoparticles into their (Ni-P) matrix. In the present study, Ni-P-Ti nanocomposite coatings have been developed on high strength low alloy steel (HSLA) through electroless deposition technique. For this purpose, various concentrations of titanium (Ti) nanoparticles are used in the deposition bath containing 0.0g/L, 0.25g/L, 0.5g/L, 0.75g/L, and 1.0g/L nanoparticles. XDR, SEM, microhardness, and nanoindentation have been carried out to elucidate the role of Ti nanoparticle concertation on the microstructure and mechanical properties of the Ni-P-Ti composite coatings. XRD and EDX results confirm the incorporation of nanoparticles into the Ni-P matrix during deposition processing. SEM and AFM results exhibit the formation of a dense, uniform coating without any observable defects. An increase in the mechanical properties of the Ni-P matrix was observed by the addition of Ti nanoparticles. Superior mechanical properties were shown by the samples containing 0.5g/L Ti nanoparticle concentration. Improvement in the structural, as well as mechanical properties of Ni- P matrix by the addition of Ti, confirms the suitability of Ni-P-Ti composite coatings for various engineering applications.

Abstract The purpose of this study is to investigate the microstructure and wear resistance of plasma sprayed WC-Co-Ni coatings. WC-Co-Ni composite powders were prepared by mixing of WC powder, Co powder and a Ni-P alloy powder, followed by sintering and crushing to improve the properties of plasma sprayed WC-Co coatings. In this study, their coatings were deposited by the atmospheric plasma spraying. The evaluation of their coatings were carried out by the observation of microstructure, measuring of microhardness values, adhesion strength values and an abrasive wear test. The abrasive wear resistance of the as-sprayed WC-Co-Ni coatings was comparable with that of WC-Co coatings deposited by HVOF spraying, and besides, the properties of the post-treated WC-Co-Ni coating were comparable with those of cemented carbides.

This paper aims to gain an insight into the correlation between the microstructure and surface composition of electroless Ni-P and its behaviour during soldering with Pb free alloys including Sn-3.8Ag-0.7Cu, Sn-3.5Ag and Sn-0.7Cu. Ni-P coatings with different P contents were produced through an industrial process on copper metal substrates. The surface morphology of these coatings was observed by Scanning Electron Microscopy (SEM) and the bulk composition was analyzed by means of Energy Dispersive X-ray analysis (EDX). The mechanical properties of the coatings were evaluated by nano-indentation testing under different maximum loads. However, to understand the behaviour of P in Ni-P coatings and deterioration of the coating surfaces during exposure to air, the surfaces of the coatings were also characterised by X-ray Photoelectron Spectroscopy (XPS) for storage at different temperatures. The dependence of the solderability of Ni-P coatings on the storage time and temperature was investigated by wetting balance testing, using an inactive or active flux with or without an inert N2 atmosphere. Finally, the solderability of Ni-P coatings to Pb free solders is correlated with their composition and microstructure (e.g. surface characteristics).

Turbine inlet temperatures have now approached 1650°C (3000°F) at maximum power for the latest large commercial turbofan engines, resulting in high fuel efficiency and thrust levels approaching or exceeding 445 kN (100,000 lbs.). High reliability and durability must be intrinsically designed into these turbine engines to meet operating economic targets and ETOPS certification requirements. This level of performance has been brought about by a combination of advances in air cooling for turbine blades and vanes, computerized design technology for stresses and airflow and the development and application of rhenium (Re) containing, high γ′ volume fraction nickel-base single crystal superalloys, with advanced coatings, including prime-reliant ceramic thermal barrier coatings (TBCs). Re additions to cast airfoil superalloys not only improve creep and thermo-mechanical fatigue strength but also environmental properties, including coating performance. Re slows down diffusion in these alloys at high operating temperatures.(1) At high gas temperatures, several issues are critical to turbine engine performance retention, blade life and integrity. These are tip oxidation in particular for shroudless blades, internal oxidation for lightly cooled turbine blades and TBC adherence to both the airfoil and tip seal liner. It is now known that sulfur (S) at levels < 10 ppm but > 0.2 ppm in these alloys reduces the adherence of α alumina protective scales on these materials or their coatings by weakening the Van der Waal’s bond between the scale and the alloy substrate. A team approach has been used to develop an improvement to CMSX-4® alloy which contains 3% Re, by reducing S and phosphorus (P) levels in the alloy to < 2 ppm, combined with residual additions of lanthanum (La) + yttrium (Y) in the range 10–30 ppm. Results from cyclic, burner rig dynamic oxidation testing at 1093°C (2000°F) show thirteen times the number of cycles to initial alumina scale spallation for CMSX-4 [La + Y] compared to standard CMSX-4. A key factor for application acceptance is of course manufacturing cost. The development of improved low reactivity prime coats for the blade shell molds along with a viable, tight dimensional control yttrium oxide core body are discussed. The target is to attain grain yields of single crystal CMSX-4 (ULS) [La + Y] turbine blades and casting cleanliness approaching standard CMSX-4. The low residual levels of La + Y along with a sophisticated homogenisation/solutioning heat treatment procedure result in full solutioning with essentially no residual γ/γ′ eutectic phase, Ni (La, Y) low melting point eutectics and associated incipient melting pores. Thus, full CMSX-4 mechanical properties are attained. The La assists with ppm chemistry control of the Y throughout the single crystal turbine blade castings through the formation of a continuous lanthanum oxide film between the molten and solidifying alloy and the ceramic core and prime coat of the shell mold. Y and La tie up the < 2 ppm but > 0.2 ppm residual S in the alloy as very stable Y and La sulfides and oxysulfides, thus preventing diffusion of the S atoms to the alumina scale layer under high temperature, cyclic oxidising conditions. La also forms a stable phosphide. CMSX-4 (ULS) [La + Y] HP shroudless turbine blades will commence engine testing in May 1998.

The welding of high strength steels in general, and for pipeline fabrication in particular, has shown that cracking due to hydrogen absorption during welding is more complex in these steels than in older, lower strength steels. In older steels, primary strengthening was accomplished with carbon, which caused hydrogen cracking in the base metal HAZ under reasonably predictable conditions involving microstructure, residual stress and hydrogen level. Pipeline steels were and are in the vanguard of change in strengthening philosophy. The change involves two areas of steel making, chemical composition and deformation processing. Pipeline steels now contain low carbon levels, in many cases less than 0.10%, and the resulting lack of strength is reclaimed by adding higher alloy levels to promote solution hardening (e.g. Mn), precipitation hardening (e.g. Cb, Cu) or transformation hardening (e.g. MO). In addition, alloy elements are added to improve toughness at high strength levels (e.g. Ni). At the same time, improvements have been made in reducing impurity and residual element levels, notably for S, P and O and N. Limitations on the effects of alloying additions on strength and toughness encouraged the use of deformation processing, primarily during rolling, to promote fine-grained microstructures to increase strength andtoughness simultaneously. Electrodes for the SMAW process have been developed for welding high-strength pipeline steels by using core wires made from high-strength microalloyed skelp extruded with cellulosic (Exx10) and low hydrogen (Exx16) flux coatings. The required alloy elements for high-strength deposits were therefore obtained from the core wire and not ferroalloy powders added to the flux, as is standard industrial practice. The idea behind this change was two fold: to avoid the possibility of introducing impurities from the varying sources of ferro alloy powders, including oxygen from the oxidized powder surfaces, and also to provide a closer match of the microalloy level to modern pipeline steel chemistries. The unknowns in this work were the effects of lower impurities/similar alloy content on the mechanical properties in the cast microstructure of a weld, compared to a pipe, and of the effect on electrode welding behaviour of a flux containing no ferro powders other than FeSi.